General Integrated Solid Waste Co-Digestion Model

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water research 43 (2009) 2717–2727

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journal homepage: www.elsevier.com/locate/watres

GISCOD: General Integrated Solid Waste Co-Digestion model

Usama Zahera,*, Rongping Lia,b, Ulf Jeppssonc, Jean-Philippe Steyerd, Shulin Chena
a
Department of Biological Systems Engineering, Washington State University, P.O. Box 646120, Pullman, WA 99164-6120, USA
b
Department of Environmental Engineering, Beijing University of Chemical Technology, 100029 Beijing, PR China
c
Department of Industrial Electrical Engineering and Automation, Lund University, Box 118, SE-22100, Lund, Sweden
d
INRA, UR 50, Laboratoire de Biotechnologie de l’Environnement, Avenue des Etangs, F-11100 Narbonne, France

article info abstract

Article history: This paper views waste as a resource and anaerobic digestion (AD) as an established
Received 22 December 2008 biological process for waste treatment, methane production and energy generation.
Received in revised form A powerful simulation tool was developed for the optimization and the assessment of
11 March 2009 co-digestion of any combination of solid waste streams. Optimization was aimed to
Accepted 14 March 2009 determine the optimal ratio between different waste streams and hydraulic retention time
Published online 21 March 2009 by changing the digester feed rates to maximize the biogas production rate. Different
model nodes based on the ADM1 were integrated and implemented on the Matlab-Simu-
Keywords: linkÒ simulation platform. Transformer model nodes were developed to generate detailed
ADM1 input for ADM1, estimating the particulate waste fractions of carbohydrates, proteins,
Co-digestion lipids and inerts. Hydrolysis nodes were modeled separately for each waste stream. The
Hydrolysis fluxes from the hydrolysis nodes were combined and generated a detailed input vector to
Integrated modeling the ADM1. The integrated model was applied to a co-digestion case study of diluted dairy
Solid waste manure and kitchen wastes. The integrated model demonstrated reliable results in terms
Transformer model of calibration and optimization of this case study. The hydrolysis kinetics were calibrated
for each waste fraction, and led to accurate simulation results of the process and prediction
of the biogas production. The optimization simulated 200,000 days of virtual experimental
time in 8 h and determined the feedstock ratio and retention time to set the digester
operation for maximum biogas production rate.
Published by Elsevier Ltd.

1. Introduction (Garcı́a de Cortázar and Monzón, 2007), and suggested as


a common interface model for solid waste management (bou
This paper presents GISCOD, a general integrated solid waste Najm and El-Fadel, 2004).
co-digestion model. The main goal of this study was to A general co-digestion model is needed to support opera-
develop and test a simulation tool of the anaerobic digestion tion decisions at full-scale plants and to assist co-digestion
(AD) process that is applicable to any combinations of waste research. The AD process is a widely applicable technology to
streams using the simulation platform Matlab-SimulinkÒ. The treat and convert an organic waste stream to methane for
MatlabÒ simulation platform was used for implementation of green energy production. At wastewater treatment plants,
the risk assessment of gas emissions from solid waste incin- trucked-in wastes are digested with wastewater sludge for
erators (Kumar et al., 2009) and modeling solid waste landfills renewable energy production (Wallis et al., 2008; Zupancic

* Corresponding author. Fax: þ1 509 335 2722.


E-mail addresses: zaheru@wsu.edu (U. Zaher), ulf.jeppsson@iea.lth.se (U. Jeppsson), steyer@supagro.inra.fr (J.-P. Steyer), chens@
wsu.edu (S. Chen).
0043-1354/$ – see front matter Published by Elsevier Ltd.
doi:10.1016/j.watres.2009.03.018
2718 water research 43 (2009) 2717–2727

et al., 2008) as part of municipal policies for climate change and inerts concentrations with the proximate analysis of 17
mitigation and reduction of green house gas emissions. Biogas solid wastes (Zaher et al., 2009). In the research work pre-
plants co-digest different solid waste feedstock to increase sented in this paper, the interface procedure is generalized
biogas production. However, random or heuristic decision on and implemented with GISCOD in Matlab-Simulink as
the ratio between waste streams or feedstock to full-scale a general transformer model that interface ADM1 to any
plants often lead to process upset and significant reduction of combination of co-digested wastes. The influxes of the model
methane production (Steyer et al., 2006). The general model components from each waste are evaluated dynamically. The
would support such full-scale operation decisions. Significant hydrolysis parameters are considered separately for each
research effort was devoted during the last 5 years to study the waste and uncoupled from the hydrolysis of the decaying
co-digestion of different combinations of municipal, indus- biomass. Therefore, the GISCOD modeling tool is generalized
trial, agricultural and farming waste streams. A general model to study the co-digestion of any combination of different
is needed to define optimal co-digestion experiments sparing wastes and to evaluate their independent hydrolysis rates and
research efforts of experimental trials, and to simulate AD operation settings, i.e. their optimal feed ratio and hydraulic
improvement mechanisms that are achieved by co-digestion retention time (HRT).
such as buffered pH, reduced inhibition, improved hydrolysis
and/or adjusted C/N ratio. Improvement mechanisms of
co-digestion can be simulated by the ADM1, International 2. Methods
Water Association Anaerobic Digestion Model number 1,
which was developed by the task group on anaerobic digestion 2.1. Process model
(Batstone et al., 2002). However, the ADM1 application has
practical problems related to the characterization of the The AD process was modeled using the ADM1 (Batstone et al.,
digester feedstock and the associated model definition of the 2002) as a basis with phased implementation to separate the
enzymatic disintegration and hydrolysis steps. enzymatic hydrolysis of solid wastes from the metabolic
A generalized and separate approach is required to solve reactions utilizing soluble substrates. The ADM1 model starts
the solid waste characterization problems compared to Acti- with a disintegration step of composite particulate material,
vated Sludge (AS) for two reasons. Firstly, ADM1 is considering i.e. decomposition of feed or decaying biosolids according to
constant composition of particulates with fixed fraction their predefined fractions and composition of carbohydrates,
parameters to carbohydrates, proteins, lipids and inerts. On proteins, fat (lipids) and inerts. The second step is enzymatic
the contrary, solid wastes are heterogenic and dynamically hydrolysis of disintegrated carbohydrates, proteins and fat
changing in composition. Secondly, the lumped composite (lipids), which is the start of the corresponding three path-
particulate model component is used as the first model input ways of anaerobic degradation. The anaerobic degradation is
and, simultaneously, as a product from the model decay done in three main stepsdacidogenesis, acetogenesis and
processes. This implies that the fraction parameters and methanogenesis. The degradation steps are modeled by
hydrolysis rates of the feed substrate should match the uptake kinetics of different substrates by seven bacterial
composition and hydrolysis rates of the decaying biomass. In groups. The decay processes of the seven bacterial groups are
fact, the ADM1 was originally developed with focus on the also considered and the decaying particulates are sent back to
application of AS digestion assuming similar composition of the disintegration step.
the aerobic and anaerobic bacteria. Under this assumption, The implemented GISCOD model shown in Fig. 1 is
there is no conflict between the feed substrate and the generalized to consider the degradation of any other wastes
produced substrate from decaying bacteria. In this particular that are different in composition compared to the assumed
case, cell lysis (disintegration) is the limiting hydrolysis step. biosolids (i.e. decaying bacteria). Each waste would have
Such an assumption was proven to be consistent for plant- different fractions of carbohydrates, proteins, lipids and inerts
wide modeling since the AS inert fraction remains inert under that may be changing dynamically (Lübken et al., 2007). Each
anaerobic conditions (Ekama et al., 2007). waste would also have different hydrolysis rates of carbohy-
In previous applications of the ADM1, fraction parameters drates, proteins and lipids (Fezzani and Cheikh, 2008a,b).
were estimated from experimental data (Fezzani and Cheikh, Carbohydrates, proteins and lipids hydrolysis of each waste is
2008a,b) or evaluated as function of VS influx (Lübken et al., considered in separate model nodes. The disintegration step
2007). Using a priori expert knowledge about expected waste- was not considered for solid wastes assuming that enzymes
water characteristics and experimental measurements to can diffuse in the woven structure of wastes and hydrolysis
estimate fraction parameters is generally applied for would take place before disintegration. No cell lysis is required
modeling wastewater treatment systems (Grau et al., 2007). for solid wastes compared to AS or decaying bacteria. The
Applying such a procedure to co-digestion is not feasible since hydrolysis products are combined and used as input to
it is difficult to find unique parameter values that are appli- a single digestion node where all biological reactions of ADM1
cable to all possible combinations and ratios of solid wastes are activated. The non-hydrolyzed fractions are fed through
together with decaying anaerobic biomass. the digestion node as a dummy vector and hydrolysis kinetics
Parameter estimation problems and use of fraction in the digestion node are only applied to the decaying
parameters could be avoided using a dynamic interface to biosolids. The complete structure of ADM1 is considered in the
ADM1 to simulate AD of animal manure and solid waste hydrolysis nodes to allow future expansion of the co-digestion
(Zaher and Chen, 2006). The interface procedure was validated model considering more complex hydrolysis kinetics. The
by comparing the estimated carbohydrates, proteins, lipids other biological reactions are deactivated for the hydrolysis
water research 43 (2009) 2717–2727 2719

Fig. 1 – The GISCOD model in Matlab-Simulink.

nodes simply by assuming zero uptake, disintegration, decay Kleerebezem and van Loosdrecht (2006) used practical char-
and gas transfer rates. acteristics such as COD, Total Kjeldahl Nitrogen (TKN), etc. to
In addition to the biological reactions, the ADM1 imple- characterize the ADM1 influent. They assumed the digester’s
mentation considers the chemical equilibrium of all ions to feedstock as a single composite particulate (Xc) with constant
evaluate the pH change. The chemical equilibrium of volatile composition and used the practical characteristics to estimate
fatty acids (VFA), the carbon and nitrogen systems is solved ADM1 fraction parameters that distribute Xc after disinte-
externally once for all hydrolysis and digestion nodes. The gration to particulate components of carbohydrates, proteins
solution of chemical equilibrium is performed algebraically and lipids. The use of the fraction parameters does not allow
according the ADM1–DAE implementation (Rosen et al., 2006). dynamic simulation due to changes in the feedstock compo-
The ADM1–DAE implementation removes stiffness from the sition. The transformer model applies CBIM to estimate the
original ADM1 Ordinary Differential Equations (ODE) system influxes to ADM1 and avoids the overuse of fraction parame-
to simulate rapid dynamic changes in the anaerobic digestion ters to allow dynamic simulation. The transformer model
process, e.g. due to changing composition of the digester robustness is increased by updating the CBIM procedure to
feedstock. maximize the conversions to ADM1 components in a pre-
defined order. COD and charge balances, and the continuity of
2.2. Transformer model all CHNOP elements are checked after the conversion of each
component. Such an ordered maximization procedure was
A general transformer model to interface ADM1 to different suggested by Copp et al. (2003) to interface Activated Sludge
solid waste streams was programmed in C and incorporated Model no.1 (Henze et al., 1987) ASM1 with ADM1, maintaining
in the GISCOD Matlab-Simulink model as a C-MEX S-Function. the COD and N balances. Most recently, Nopens et al. (in press)
The general transformer model is based on the ADM1 inter- modified the Copp et al. (2003) ASM1–ADM1 interface. They
face to solid wastes (Zaher and Chen, 2006; Zaher et al., 2009). increased the robustness of the ASM1–ADM1 conversions by
The transformer model combines the advantages of previous changing the maximization order of ADM1 components for
interfacing methodologies applied to ADM1. the co-digestion of secondary sludge (from ASM1) with
primary sludge (from primary settler). The conversions from
2.2.1. Implemented interfacing advantages ASM1 to ADM1 were extended to include carbohydrates,
The general transformer model represents an enhancement proteins and lipids instead of Xc. Proteins were maximized
of the Continuity Based Interfacing Methodology (CBIM) using Total Kjeldahl Nitrogen (TKN) and the remaining
(Vanrolleghem et al., 2005). The CBIM applies Chemical particulate COD was distributed between carbohydrate and
Oxygen Demand (COD) balance, charge balance and elemental lipids using fraction parameters. Extending the balance rela-
continuity to all macronutrient elements CHNOP to connect tions in the transformer model eliminates the use of fraction
different models (Volcke et al., 2006; Zaher et al., 2007). The parameters. The transformer model is upgraded in the
CBIM in the general transformer is applied to interface the implementation with GISCOD to allow the user to change the
ADM1 to practical characteristics of solid wastes. maximization order of ADM1 components without changing
2720 water research 43 (2009) 2717–2727

the transformer model algorithm. The maximization order is 2. rz is verified using the conditions imposed by Eq. (5). If
implemented as a one-dimensional array parameter to the shown true, the next rzþ1 was calculated starting from step
transformer S-function to increase the generality of the 1 above;
transformer model for the application to any solid waste. 3. If shown false, rz is changed and calculated according to Eq.
(6), the rz calculation is then terminated and other rates (ri,
2.2.2. Transformer algorithm i ¼ z þ 1:n) are assigned a value of 0;
The transformer model transforms a set of practical 4. Any remaining fluxes are added to the relevant inorganic
measurements to the input vector of ADM1 according to the components; and accordingly,
stoichiometry presented in Table 1. Table 1 consists of four 5. All practical measurements are mapped to the new vector
panes. The lower two panes shows the assumed composition r. The output flux of substrate composition is then calcu-
of the practical measurements on the left, components 1 to 11, lated using Eq. (3).
and the composition of the estimated ADM1 input compo-
nents on the right. The upper two panes represent the stoi-
chiometry nj;k for the conversions j and the elements k. The
stoichiometry is evaluated by mass and charge balances P !
Influxk  z1 i¼1 ni;k ri
according to Eq. (1). The stoichiometry matrix is uploaded to rz ¼ (4)
nz;k
the Matlab work space as a two-dimensional array parameter
to transformer model S-function.
X X
z
nj;k ij;Comp ¼ 0 with Comp ¼ Thod; C; N; H; O; e (1) nz;k rz < Influxk for k ¼ 1 : P (5)
k 1

The transformation step in CBIM was changed to include the  


 
ordered maximization procedure. The original transformation  P 
Influxk  z1 n r 
of CBIM is generated by Eqs. (2) and (3). A set of algebraic 
rz ¼ min i¼1 i;k i 
for k ¼ 1 : P (6)
n 
 z;k 
equations is generated by Eq. (2) to map the influxes to vector  
rj, j ¼ 1:n where n is the number of conversions, using the
stoichiometry in the left pane of the transformation matrix,
i.e., for k ¼ 1:P where P is the number of practical measure- 2.3. Integrated co-digestion model
ments. Then Eq. (3) calculates the outfluxes from rj using the
stoichiometry in the right pane of the transformation matrix, The different models integrated in GISCOD are written in C
i.e., k ¼ P þ 1:P þ Q where Q is the number of the estimated and compiled in Matlab as MEX S-functions to run simulations
composition components. and optimizations using the Matlab-Simulink platform and its
toolboxes. The compiled version of the model works with
X
n
most Matlab-Simulink (release 14) installations on Windows
nj;k rj ¼ Influxk for k ¼ 1 : P (2)
j¼1 XP and VISTA operating systems.
The practical characteristics and flows of all different
X
n solid wastes as well as all model parameters are arranged in
Outfluxk ¼ nj;k rj for k ¼ P þ 1 : P þ Q (3) Microsoft Excel file. All inputs, initial states and parameters
j¼1
to the co-digestion models are read from the Excel file into
In the implementation for the co-digestion model Eq. (2) is the Matlab work space using an automated Matlab script.
replaced by a maximization procedure according to Zaher The simulation starts from Simulink after configuring the
et al. (2009) to increase the transformer robustness, to conceal numerical solution using any variable step solver that is
(correct) possible errors in the practical measurements and to available in Simulink. Fig. 1 shows the scheme of GISCOD in
maintain the elemental mass balance during the conversions. Matlab-Simulink. Practical characteristics and flows of each
The elements of the vector rj are maximized in a predefined solid waste are inputs from the workspace to the transformer
order to make sure that the elemental influxes sourced by the model nodes. The practical characteristics are converted to
input of practical measurements are sufficient before calcu- the complex composition of the ADM1 input state vector and
lating the next element of rj. A predefined order of rz, z ¼ 1:10, assigned to the input of separate hydrolysis nodes. The
which corresponds to j ¼ (10, 5:9, 4, 3, 1, 2), maximizes the hydrolysis output signals are rearranged by the combiner
conversion to inert particulates, volatile fatty acids, sugars, model, which generates the input to the ADM1 node. The
lipids, proteins, carbohydrates, and then inorganic compo- combiner model divides the solid wastes AD process into an
nents. This maximization order is uploaded before simulation enzymatic hydrolysis phase in the hydrolysis nodes only and
to the Matlab work space as a parameter to the transformer an uptake phase of the hydrolysis products in the ADM1
model S-function. Thus, the maximization order can be easily node. Thus, Solids Residence Time (SRT) of each waste is
changed by the user. The maximization is done according to considered separately for each hydrolysis node according to
the following steps: the time its particulate components are allowed to stay in the
digester (i.e. according mixing patterns) in addition to the
1. rz is calculated using Eq. (4) as a function of the influx of the time of any pre-hydrolysis steps. The combiner node passes
most correlated measurement k, i.e., corresponding to the the non-hydrolyzed particulates as dummy variables to the
unique value of nz,k ¼ -1 at each conversion; ADM1 and sums other variables on the basis of fluxes from
Table 1 – Calculated transformation and composition matrices of the transformer model.

water research 43 (2009) 2717–2727


2721
2722 water research 43 (2009) 2717–2727

both waste streams. In the ADM1 node, non-hydrolyzed feeding. The only degree of freedom used during the experi-
portions are not subject again to the hydrolysis kinetics and ment was the daily feed rates, which were varied for each
the hydrolysis in the ADM1 node is only considered for experiment according to the profiles shown in Fig. 2. The
particulate fractions of the decaying biosolids (bacteria). reactors for both experiments were completely mixed and
Thus, the digester out-flux contains non-hydrolyzed carbo- arranged to have a hydrolysis step of 0.6 L volume followed by
hydrates, proteins and lipids originating from the solid a digestion step of 2 L. All reactors were kept at 35  C. The gas
wastes in addition to the corresponding components result- production from both steps was used for calibration. First, the
ing from decaying biosolids. Thus the mass balance is manure hydrolysis parameters were estimated from the
maintained. The ADM1 is solved at each time step and the manure only digestion experiment. Secondly, the kitchen
output is stored in the Matlab workspace. The chemical waste hydrolysis parameters were estimated from the co-
equilibrium is solved in the ADM1 model node and the digestion experiment. Carbohydrates, proteins and lipids
evaluated ions and pH are shared with the hydrolysis nodes. were analyzed for each waste to validate the transformer
The pH calculation is linked to the hydrolysis nodes to allow predictions. Carbohydrates were quantified by sequential
future extension of the hydrolysis kinetics to reflect the pH extraction using neutral and acid detergent, followed by
dependency of the hydrolysis. Although the optimal pH of strong acid extraction. Proteins were analyzed by the Lowry
methanogenesis is around pH 7.0, the optimum pH of colorimetric method calibrated on bovine serum albumin.
hydrolysis and acidogenesis is between pH 5.5 and 6.5 (Ward The lipids content was determined by a Soxhlet method using
et al., 2008). petroleum ether for extraction.
Optimization of the solid waste ratio and HRT was done by
2.4. Calibration and optimization case study simulating several virtual experiments using the calibrated
model. The optimal ratio and HRT were determined by
GISCOD robustness and simulation speed were tested by comparing the steady state biogas flow rate from such virtual
running the model in parameter estimation and optimization experiments. Virtual experiments of 200 cases were simu-
algorithms. Parameter estimation was done using SimulinkÒ lated varying the ratio of kitchen waste, flow and methano-
Parameter EstimationÔ software and the simplex optimiza- genic reactor volume. Ten retention times were considered 5,
tion algorithm (Nelder and Mead, 1965). Two experiments of 7.5, 10, 15, 20, 50, 75, 100, 150 and 200 days. The kitchen waste
digesting manure alone and manure with kitchen waste were ratio was varied from 5% to 100% in 5% increments. The
performed to calibrate the hydrolysis parameters for each hydrolysis volume was 2 L for all the simulated cases. Two
waste. Both waste average characteristics are listed in Table 2. methanogenic volumes were considered: 2 L with HRT
Only the indicated 11 characteristics are needed as model 20 days and 20 L for longer HRT. Each case was simulated
inputs. It was not possible to digest food waste alone due to until the gas flow rate reached a steady state after 1000 days
acidification and pH drop. Both wastes were homogenized of simulation time, i.e. a total virtual experimental time of
and kept frozen in batches that were only thawed before 200,000 days.

Table 2 – Characteristics of diluted manure and kitchen waste.


Characteristics Co-digestion Unit Diluted manure waste Kitchen waste
model input no.

Total Chemical Oxygen Demand (CODt) (gCOD m3) 27217 380647


Particulate COD (CODp) 1 (gCOD m3) 23550 368400
Soluble COD (CODs) (gCOD m3) 3667 12247
Soluble COD without VFA COD(CODs-VFA) 2 (gCOD m3) 2521 3500
Volatile Fatty Acids (VFA) 3 (gCOD m3) 1146 8747
Total Carbon (TC) (gC m3) 10064 139760
Total Organic Carbon (TOC) 4 (gC m3) 9340 139280
Total Inorganic Carbon (TIC) 9 (mol HCO 3
3 m ) 60 40
Total Kheldal Nitrogen (TKN) (gN m3) 882 15300
Total Organic Nitrogen (Norg) 5 (gN m3) 598 14000
Total Ammonia Nitrogen (TAN) 6 (gN m3) 284 1300
Total Phosphorous (TP) (gP m3) 219 1606
Organic Phosphorus (TP-orthoP) 7 (gP m3) 187 720
Ortho-Phosphate (orthoP) 8 (gP m3) 32 886
Total alkalinity (S cations) 10 (equ m3) 60 25
Total Solids (TS) (g m3) 20697 291000
Fixed Solids (FS) 11 (g m3) 5397 31000
Total Volatile Solids (TVS) (g m3) 15300 260000
Carbohydrate (g m3) 10924  428 153400  11180
Protein (g m3) 4069  367 85800  8320
Lipids (g m3) 306  61.2 20800  2860
water research 43 (2009) 2717–2727 2723

Manure Flow Experiment 1 Manure Flow Experiment 2


0.7 0.060
Kitchen Waste Flow Experiment 2

0.6
0.050

Kitchen Waste Feed L/day


0.5
Manure flow L/day 0.040

0.4
0.030
0.3

0.020
0.2

0.010
0.1

0 0.000
0 20 40 60 80 100
Time days

Fig. 2 – Daily feed rates implemented in the calibration experiments.

extraction method is an accurate standard method to break


3. Results and discussion the crystal structure of fiber, which is the main form of
carbohydrates in manure. The starch content is high in
3.1. Transformer output kitchen waste but would not be quantified as accurately as
fiber with the same extraction method. Using the carbohy-
Among other ADM1 input state variables, carbohydrates, drate measurements as a direct input to the ADM1 model
proteins and lipids were estimated in COD units by the trans- would have introduced an error to the carbon balance kept
former model. The ADM1 model uses COD units for organic within the model. Therefore, using the transformer model
components and bacterial species to maintain the COD was necessary to keep the carbon balance.
balance. The corresponding g/L concentration was evaluated Proteins: Measured and estimated protein contents were
according to the defined composition of ADM1 components in more consistent in the case of kitchen waste as compared to
Table 1 and compared to the measured concentrations in Fig. 3. the case of manure. The measuring method was calibrated
Generally, the estimated and measured concentrations were using bovine serum albumin, which is more relevant to the
consistent in terms of distribution among the three main kind of proteins that normally exist in kitchen wastes, such
particulate components. However, some differences could be as beef or whey. Using the protein measurements for
observed for each individual component when comparing the manure as a direct input to ADM1 model would have
results for the manure and kitchen waste. introduced errors to the nitrogen balance. Nitrogen in solids
Carbohydrates: Estimated carbohydrates content was wastes is mainly sourced by the particulate proteins. The
consistent with measured data in the case of manure but it use of the transformer model maintained the nitrogen
was higher in the case of kitchen waste. The detergent balance.

Fig. 3 – Comparison of the measured and the estimated compositions by the transformer model for diluted manure (left) and
kitchen waste (right).
2724 water research 43 (2009) 2717–2727

Lipids: Lipids were the smallest fraction of particulates in respectively. The longer and more dynamic experiment no. 2
both wastes. The estimated and measured lipids contents of co-digestion required 1 min 30 s CPU-time using the same
were relatively inconsistent. On one hand, the estimated simulation settings using a standard 3 GHz PC. The efficient
lipids composition was assumed to be in the form of phos- simulation time was achieved because of the separate alge-
pholipids but other forms may exist in both wastes. On the braic solution of the chemical equilibrium. The maintenance
other hand, Soxhlet extraction is highly biased if the sample of COD and elemental mass balances using the transformer
matrix is mainly non-lipids (Manirakiza et al., 2001). contributes to the simulation accuracy, which also contrib-
Generally, the use of the transformer model within GISCOD utes to improved simulation speed.
maintains the continuity of COD and elemental mass that are
essential to guarantee accurate and reliable simulation. Direct 3.3. Calibration of hydrolysis kinetics
measurements of the waste particulate fractions would not
achieve the same reliability. The analytical methods are With the reliable simulation speed, it was possible to run the
dependent on the types of the particulate fractions, which are model using the simplex optimization algorithm for calibra-
unknown for wastes and are often different from the types tion purposes. Fig. 4 shows the predictions of biogas flow rate
defined in the model stoichiometry. after model calibration, which are comparable to the
Maintaining accurate carbon and nitrogen balances during measurements. The hydrolysis rates of carbohydrates,
the simulation is necessary since the C:N ratio is a key factor proteins and lipids were estimated by fitting the biogas
affecting the co-digestion of different waste streams measurements from experiment 1, digesting diluted manure
(Hartmann and Ahring, 2005; Yen and Brune, 2007; Zhang only. The estimated rates were 0.019, 0.025, 0.022 d1,
et al., 2008; Shanmugam and Horan, 2009). Also, the C and N respectively, for diluted manure waste. These rates are
elemental continuity preserved in the GISCOD model is considerably lower compared to the default values of ADM1
important when linking the AD model to other existing (10 d1 for each particulate component) that were originally
models of subsequent unit processes or for integrated designated for the hydrolysis of activated aerobic sludge and
assessment. For instance elemental continuity is the key are still used in GISCOD for the hydrolysis of the decaying
mechanism to evaluate pH and chemical equilibrium anaerobic bacteria after a disintegration step (rate kdis ¼ 0.5). It
variables, such as CO2/HCO þ
3 and NH4 /NH3 in the AD process is noteworthy that the default hydrolysis rates presented in
out-flux. The evaluation of CO2 and NH3 emissions allows the ADM1 in 2002 is now considered to be at least a factor of
further assessment of subsequent unit processes, such as ten too large also by the ADM1 Task Group (Batstone, 2008:
emission studies from composting (Paillat et al., 2005; Komilis personal communication). The low rates indicate that the
and Ham, 2006), drying (Deng et al., 2009) and landfill facilities digestion of the manure waste was limited by hydrolysis and
(He et al., 2006). Furthermore, estimation of the pH and NHþ 4 as that the amount of methane produced was mainly from
well as phosphorusdevaluated from the mass balance in the soluble COD digestion. When the diluted manure was co-
transformer modeldallows more integrated assessment, digested with kitchen waste the biogas production was
such as studies evaluating added fertility to soils from waste significantly increased even at periods of similar HRT in both
application (Alvarenga et al., 2007; Kang et al., 2008) or eval- experiments, i.e. day 0 to 38 and day 63 to 73. The higher
uating leachate pollution to water bodies (Singh et al., 2005). biogas production was not only due to the higher COD load of
added kitchen waste but also because the particulate fractions
3.2. Simulation speed of the kitchen waste were easily hydrolysable. The estimated
hydrolysis rates of the kitchen waste from the second exper-
The simulation speed was kept low despite the added model iment were 5.22, 1.86 and 1.24 d1 for carbohydrates, proteins
complexity of separate hydrolysis and transformation model and lipids, respectively. This indicates the necessity of sepa-
nodes. The 73 days simulation of manure digestion required rating the hydrolysis of both wastes. In a similar co-digestion
less than 1 min CPU-time using the ode15s solver in Simulink study of a fixed ratio 80:20 manure liquids to cow fodder
with 1E-7 and 1E-6 relative and absolute tolerance, (Lübken et al., 2007), the best ADM1 simulation of biogas

Co-digestion (simulation) Co-Digestion (data) Manure Only (simulation) Manure Only (data)

8 7.4
Gas flow rate (L/day)

7 7.3
6 7.2
5 7.1
7
pH

4
6.9
3
6.8
2 6.7
1 6.6
0 6.5
0 20 40 60 80 100 120 0 20 40 60 80 100 120
days days

Fig. 4 – Comparison of simulated and measured biogas production (left) and pH (right) after calibration of the hydrolysis
parameters.
water research 43 (2009) 2717–2727 2725

prediction matched the experimental data at 0.3 d1 hydro- 50 days did not produce any increase in the daily gas
lysis rate for the three particulate fractions. The slightly production since the process was rate limited by the COD
higher hydrolysis rate compared to digesting manure is due to loading rate. At HRT <20 days the process was limited by the
the addition of the cow fodder. Cow fodder hydrolysis rate is methanogenesis step since 2 L volume was assigned to both
higher compared to manure that has already been passed hydrolysis and methanogenesis steps. There was another
through hydrolysis and digestion in the rumen. For reliable local optimum of biogas production at HRT of 10 days that was
simulation and prediction of the biogas production at variable mainly related to soluble substrates and not the particulate
ratios of co-digested wastes, accurate hydrolysis rates should substrate. Inhibition due to VFA accumulation and pH started
be estimated for each waste and each particulate fraction. at HRT less than 20 days. However, the addition of diluted
Expanding the applicability of GISCOD to any waste combi- manure buffered the pH near the optimum range except for
nations allows the integrated assessment of AD using HRT <10 days. Simulations showed VFA accumulation and pH
different treatment scenarios. For instance, accurate evalua- drop at HRT <10 days. Also, at 10 days HRT and an addition of
tion of the biogas production co-digesting energy crops, agri- kitchen waste >80%, pH dropped and VFA accumulated.
cultural residues and wastes would benefit LCA studies of During VFA accumulation and pH drop, methanogenesis was
alternative processes for bio-fuel production (Tan et al., 2004) completely inhibited and biogas was mainly CO2. Methane
adding the AD process to the complete process train. and total biogas production increased with the additional
kitchen waste except at low HRT where the manure alkalinity
3.4. Simulation of chemical equilibrium could not maintain the pH in the optimal range.
The GISCOD simulated different feedstock and influent
The pH, presented in Fig. 4, was slightly higher during manure flow rates using two digester volumes to determine the
only digestion in Experiment 1 indicating that manure has optimum design and operation of an AD application to the co-
higher alkalinity than kitchen waste. During overload periods, digestion of two different waste streams. The simulation
hydraulically during manure only digestion from day 34 to day saved excessive experimental time, which would be needed to
63 and organically by increasing the food waste ratio from day determine the optimum for such co-digestion applications.
84 till the end of the co-digestion experiment, the pH dropped The determined optimal result can then be validated experi-
rapidly but the biogas production increased. During process mentally before full-scale implementation in a relatively short
overloads, VFA’s accumulate causing the pH to drop (Zaher time. More generally, the model determines virtually the
et al., 2004). The drop of the pH is caused by stripping of optimal design and operation as well as digester outputs that
alkalinity and higher CO2 production in the biogas. would benefit environmental and economic studies of AD
applications. Such model-based optimization of design and
3.5. Optimization of reactor design and operation operation settings is of a great practical advantage compared
to ‘‘random’’ or ‘‘heuristic’’ approaches that sometimes lead
The 200,000 days of virtual experimental time were simulated to severe problems. Steyer et al. (2006) illustrated the severe
using GISCOD in 8 h of CPU-time to find the optimal operation consequences of using such ‘‘heuristic’’ approaches to make
for the co-digestion case study. Fig. 5 shows the predicted gas operation decisions on full-scale biogas plants. They gave
flow rates of the model for the 200 virtual experiments of the a real example of a biogas plant co-digesting pig manure and
optimization procedure after filtering for a few anomalies due industrial wastewater in Blaabjerg, Denmark that experienced
to numerical errors and the high non-linearity of the model. a serious accident due to an overdose of the industrial waste.
The optimal biogas and methane production was found at The consequence of such single event was the significant
a HRT of 50 days using a pre-hydrolysis step of 2 L and reduction of bio-gas production and methane content. The
a digester volume of 20 L. Increasing the HRT more than process did not recover for 3 months and the biogas had to be

Fig. 5 – Biogas optimization results of manure and kitchen wastes co-digestion varying feedstock, flow and methanogenic
volume.
2726 water research 43 (2009) 2717–2727

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